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Equations-of-motion method: Potential energy curves for N2, CO, and C2H4

Coughran, William and Rose, John and Shibuya, Tai-Ichi and McKoy, Vincent (1973) Equations-of-motion method: Potential energy curves for N2, CO, and C2H4. Journal of Chemical Physics, 58 (7). pp. 2699-2709. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:COUjcp73

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Abstract

We have applied the equations-of-motion method to various states of N2, CO, and ethylene at nuclear configurations slightly distorted from the ground equilibrium geometry. This approach attempts to calculate energy differences instead of absolute energies and is thus relatively insensitive to the accuracy of the assumed ground state wavefunction. By using the experimental behavior of the ground state on distortion, we can generate accurate potential energy curves for the excited states in the region of spectroscopic interest. These curves confirm the spectroscopic behavior of the 1∑+ states of N2 and the 1∑+ states of CO where valence and Rydberg states of the same symmetry interact. The results for the T and V states of ethylene agree with experiment and show that the V state is predominantly a highly correlated valence state. Oscillator strengths across an absorption band are also accurately determined in this method. We report the dependence of the transition moment on bond length for the X1∑+→A1II transition in CO, which is in excellent agreement with experiment.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1063/1.1679571DOIUNSPECIFIED
http://link.aip.org/link/?JCPSA6/58/2699/1PublisherUNSPECIFIED
Additional Information:© 1973 American Institute of Physics. Received 14 September 1972. Work supported by the National Science Foundation. [T-I.S. was an] Alfred P. Sloan Foundation Fellow. Arthur Amos Noyes Laboratory of Chemical Physics, Contribution No, 4551.
Funders:
Funding AgencyGrant Number
National Science FoundationUNSPECIFIED
Alfred P. Sloan FoundationUNSPECIFIED
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Arthur Amos Noyes Laboratory of Chemical Physics4551
Record Number:CaltechAUTHORS:COUjcp73
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:COUjcp73
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:11842
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:08 Oct 2008 04:20
Last Modified:26 Dec 2012 10:21

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